CN106816595B - Nitrogen-doped carbon-coated ferric oxide negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Nitrogen-doped carbon-coated ferric oxide negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 54
- 229910052681 coesite Inorganic materials 0.000 claims description 40
- 229910052906 cristobalite Inorganic materials 0.000 claims description 40
- 229910052682 stishovite Inorganic materials 0.000 claims description 40
- 229910052905 tridymite Inorganic materials 0.000 claims description 40
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
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- 238000005406 washing Methods 0.000 claims description 16
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- 239000011229 interlayer Substances 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 229920000128 polypyrrole Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
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- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- -1 polyoxyethylene copolymer Polymers 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 2
- 239000001230 potassium iodate Substances 0.000 claims description 2
- 229940093930 potassium iodate Drugs 0.000 claims description 2
- 235000006666 potassium iodate Nutrition 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
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- 239000003792 electrolyte Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 235000014676 Phragmites communis Nutrition 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a nitrogen-doped carbon-coated ferric oxide negative electrode material for a lithium ion battery and a preparation method thereof. The lithium ion battery composite negative electrode material provided by the invention can keep high cycle capacity, excellent cycle stability and high rate (high current density charge and discharge) performance in a large temperature range including room temperature, and has good application prospect.
Description
Technical Field
The invention relates to a chargeable and dischargeable lithium ion battery cathode material and a preparation method thereof, belonging to the field of electrochemical power sources.
Background
In the face of the current increasingly urgent energy and environmental problems, it is urgent to develop a high-efficiency and stable lithium secondary battery. The lithium ion battery has the characteristics of high energy density, long cycle life, environmental friendliness and the like, and is widely applied to the fields of portable electronic products, power or energy storage batteries and the like. At present, the commercial lithium ion battery graphite negative electrode material has low specific capacity and poor rate performance, and has great potential safety hazard, so the development of a novel negative electrode material becomes a hotspot in the research field at present. In recent years, with the development of lithium ion batteries, it has been found that a transition metal oxide (iron sesquioxide) has the advantages of high theoretical specific capacity, rich content, no pollution and the like, and can be used as a negative electrode material of a lithium secondary battery. However, the iron sesquioxide has some disadvantages while showing outstanding advantages as a lithium battery negative electrode material: 1) bulk ferric oxide has poor conductivity and is not favorable for electron transmission; 2) in the charging and discharging process, bulk ferric oxide is easy to pulverize and agglomerate, so that the cycle performance of the battery is reduced sharply.
Therefore, a method for improving the performance of ferric oxide as a negative electrode material of a lithium ion battery is in need of being discovered.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nitrogen-doped carbon-coated ferric oxide negative electrode material for a lithium ion battery and a preparation method thereof, aiming at improving the conductivity of the material and avoiding the agglomeration phenomenon of the material so as to improve the lithium storage performance of the material.
The invention solves the technical problem and adopts the following technical scheme:
the invention discloses a nitrogen-doped carbon-coated ferric oxide negative electrode material for a lithium ion battery, which is characterized in that a silicon dioxide layer is coated on the outer surface of nano spindle-shaped ferric oxide to be used as a precursor, a layer of conductive polypyrrole is coated on the outer surface of the silicon dioxide layer, and finally the polypyrrole is carbonized through annealing, and a silicon dioxide interlayer is removed through etching, so that the nitrogen-doped carbon-coated ferric oxide negative electrode material with an interlayer gap structure is obtained.
Preferably, the long axis of the nano spindle-shaped ferric oxide is 100-3000 nm, the short axis of the nano spindle-shaped ferric oxide is 50-1800 nm, the thickness of the interlayer gap structure is 5-30 nm, and the nitrogen-doped carbon layer is amorphous graphite with the thickness of 20-35 nm; the mass percentage of the nitrogen-doped carbon in the nitrogen-doped carbon-coated ferric oxide negative electrode material is 34-45%.
The preparation method of the nitrogen-doped carbon-coated ferric oxide negative electrode material for the lithium ion battery comprises the following steps of:
A. synthesizing nano spindle ferric oxide through solvothermal reaction;
B. under the alkaline condition, coating a silicon dioxide layer on the outer surface of the nano spindle ferric oxide by a sol-gel method to obtain a spindle precursor Fe2O3@SiO2；
C. Modifying the fusiform precursor Fe by using a macromolecular surfactant2O3@SiO2Then adding pyrrole monomer and initiator to react to make the modified fusiform precursor Fe2O3@SiO2Coating a layer of conductive polypyrrole on the outer surface to obtain Fe2O3@SiO2@Ppy；
D. Subjecting the Fe to an inert gas atmosphere2O3@SiO2Annealing @ Ppy to carbonize polypyrrole to obtain Fe2O3@SiO2@C；
E. Subjecting said Fe to2O3@SiO2Etching with @ C in alkaline solution to remove SiO2Namely obtaining the nitrogen-doped carbon-coated ferric oxide cathode material Fe with the interlayer gap structure2O3@C。
The preparation method specifically comprises the following steps:
A. synthesizing nano spindle ferric oxide through solvothermal reaction:
adding ferric trichloride and sodium dihydrogen phosphate or sodium hypophosphite into a mixed solution of water and ethanol to obtain a reaction solution; the concentration of ferric trichloride in the reaction liquid is 0.015-0.02 mol/L, and the concentration of sodium dihydrogen phosphate or sodium hypophosphite is 0.1-0.5 mmol/L; in the mixed liquid of water and ethanol, the volume percentage of the ethanol is 0-50%;
and adding the reaction solution into a reaction kettle, carrying out hydrothermal reaction at 98-105 ℃ for 48-168 h, then cooling to room temperature, centrifuging, and washing to obtain the nano spindle ferric oxide.
B. Dispersing 50mg of nano spindle ferric oxide into 100-200 mL of mixed solution composed of isopropanol and water according to the volume ratio of 4:1, ultrasonically stirring for 10-60 min, then adding 1-5 mL of ammonia water and 0.1-0.6 mL of tetraethyl orthosilicate under the stirring condition, continuously stirring for 4-24 h, centrifuging and washing to obtain a spindle precursor Fe2O3@SiO2；
C. B, mixing the fusiform precursor Fe obtained in the step B2O3@SiO2Dispersing in 100mL of ethanolThen adding 0.5-3.2 g of high molecular surfactant, stirring for 12-48 h, centrifuging and washing to finish the modification of the high molecular surfactant;
the modified fusiform precursor Fe2O3@SiO2Dispersing in 25mL of deionized water, adding 0.18-0.3 mL of pyrrole monomer, performing ultrasonic treatment for 30min, dropwise adding 25mL of initiator solution with the concentration of 15-27 mmol/L under the stirring condition, performing polymerization for 4-12 h, centrifuging, washing and drying to obtain Fe2O3@SiO2@Ppy；
D. Subjecting said Fe to2O3@SiO2@ Ppy is placed in an inert gas atmosphere, the temperature is raised to 550-650 ℃ at the temperature rise rate of 2-5 ℃/min, annealing is carried out for 2-4 h, polypyrrole is carbonized, and Fe is obtained2O3@SiO2@C；
E. Subjecting said Fe to2O3@SiO2Etching with @ C in alkaline solution to remove SiO2Namely obtaining the nitrogen-doped carbon-coated ferric oxide cathode material Fe with the interlayer gap structure2O3@C。
Preferably, the polymeric surfactant is at least one of polyvinylpyrrolidone, polyacrylamide, hydroxyethyl cellulose and polyoxyethylene copolymer.
Preferably, the initiator is at least one of ammonium persulfate, ferric trichloride, hydrogen peroxide, potassium dichromate and potassium iodate.
Preferably, the alkaline solution in step E is a sodium hydroxide solution or a potassium hydroxide solution.
The invention has the beneficial effects that:
1. the composite cathode material of the lithium ion battery improves the conductivity of the active substance by compounding carbon and nitrogen, and in addition, a cavity between the nitrogen-doped carbon layer and the ferric oxide provides an effective space for the expansion of the volume of the active substance during lithium intercalation/deintercalation, thereby preventing the pulverization and agglomeration of the ferric oxide; the cathode material can keep high cycle capacity, stable cycle performance and good high-rate (high-current density charge-discharge) performance in a large temperature range including room temperature, and has good application prospect.
2. The transition metal oxide in the cathode material is ferric oxide, and the cathode material has the advantages of wide raw material source, low price, easy obtainment, simple preparation process and easy amplification.
Drawings
FIG. 1 shows the nano spindle-shaped iron sesquioxide Fe obtained in example 1 of the present invention2O3(FIG. 1(a)) and nitrogen-doped carbon-coated iron sesquioxide negative electrode material (Fe)2O3@ C) (FIG. 1 (b)).
FIG. 2 shows the nano spindle-shaped iron sesquioxide Fe obtained in example 1 of the present invention2O3Scanning electron microscope images (fig. 2(a)) and transmission electron microscope images (fig. 2 (b)).
FIG. 3 shows the N-doped carbon-coated iron sesquioxide negative electrode material (Fe) obtained in example 1 of the present invention2O3@ C) (fig. 3(a)) and transmission electron micrographs (fig. 3 (b)).
FIG. 4 shows the negative electrode material (Fe) obtained in example 1 of the present invention2O3@ C) cycle performance in lithium ion batteries.
FIG. 5 shows the N-doped carbon-coated iron sesquioxide negative electrode material (Fe) obtained in example 2 of the present invention2O3@ C) (fig. 5(a)) and transmission electron micrographs (fig. 5 (b)).
FIG. 6 shows the negative electrode material (Fe) obtained in example 2 of the present invention2O3@ C) cycle performance in lithium ion batteries.
Detailed Description
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Electricity in the following examplesThe cell performance tests all adopt a blue battery test system, and Fe in the following examples2O3Mixing and uniformly dissolving a @ C negative electrode material, Ketjen black and polyvinylidene fluoride (pVDF) in an NMP solution according to a mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper current collector (copper foil) to prepare a working electrode, taking a glass fiber membrane as a diaphragm, and selecting 1M lithium hexafluorophosphate (LiPF) as electrolyte6) The Ethylene Carbonate (EC)/dimethyl carbonate (DEC) mixed solution (volume ratio is 1:1) is assembled into a 2032 button cell in an argon-filled glove box, and the test voltage range is 0.01V-3V (vs Li)+/Li)。
Example 1
The preparation method comprises the following steps of:
A. adding ferric trichloride hexahydrate and sodium dihydrogen phosphate dihydrate into 300mL of water to obtain a reaction solution; the concentration of ferric trichloride in the reaction liquid is 0.02mol/L, and the concentration of sodium dihydrogen phosphate is 0.45 mmol/L;
and adding the reaction solution into a reaction kettle, carrying out hydrothermal reaction at 105 ℃ for 48h, naturally cooling to room temperature, centrifuging, and washing to obtain the nano spindle ferric oxide.
B. Dispersing 50mg of nano spindle ferric oxide into 200mL of mixed solution composed of isopropanol and water according to the volume ratio of 4:1, ultrasonically stirring for 30min, then adding 2mL of ammonia water and 0.2mL of tetraethyl orthosilicate under the stirring condition, continuously stirring for 4h, centrifuging and washing to obtain a spindle precursor Fe2O3@SiO2；
C. B, mixing the fusiform precursor Fe obtained in the step B2O3@SiO2Dispersing in 100mL of ethanol, then adding 3.2g of PVP, stirring for 18h, centrifuging and washing to finish the modification of the macromolecular surfactant;
the modified fusiform precursor Fe2O3@SiO2Dispersing in 25mL deionized water, adding 0.2mL pyrrole monomer, performing ultrasonic treatment for 30min, dropwise adding 25mL ferric trichloride solution with concentration of 17.8mmol/L under stirring, performing polymerization for 4h, centrifuging, washing, and drying to obtain Fe2O3@SiO2@Ppy；
D. Mixing Fe2O3@SiO2@ Ppy in argon atmosphere, heating to 600 deg.C at a heating rate of 3 deg.C/min, annealing for 4 hr to carbonize polypyrrole to obtain Fe2O3@SiO2@C；
E. Mixing Fe2O3@SiO2@ C is put into 2M sodium hydroxide solution for etching to remove SiO2Namely obtaining the nitrogen-doped carbon-coated ferric oxide cathode material Fe with the interlayer gap structure2O3@C。
FIG. 1 shows the nano spindle-shaped ferric oxide Fe obtained in this example2O3(FIG. 1(a)) and nitrogen-doped carbon-coated iron sesquioxide negative electrode material (Fe)2O3@ C) (FIG. 1 (b)).
FIG. 2 shows the nano spindle-shaped ferric oxide Fe obtained in this example2O3The scanning electron micrograph (FIG. 2(a)) and the transmission electron micrograph (FIG. 2(b)) of the product show that the product has uniform morphology, the major axis is 550nm long and the minor axis is 85nm long.
FIG. 3 shows an example of a nitrogen-doped carbon-coated iron oxide negative electrode material (Fe) according to the present invention2O3@ C) (fig. 3(a)) and transmission electron micrographs (fig. 3 (b)). The thickness of the interlayer gap structure of the material is 20nm, the thickness of the nitrogen-doped carbon layer is 30nm, the final structure is kept intact, the external carbon shell is not damaged, and the complete carbon shell can effectively prevent the agglomeration and pulverization of the ferric oxide in the charging and discharging processes, so that the cathode material has good cycling stability.
And assembling the battery according to the sequence of the negative electrode shell, the lithium sheet, the diaphragm, the electrolyte, the negative electrode, the gasket, the reed and the positive electrode shell, and carrying out performance test. FIG. 4 shows the negative electrode material (Fe) of this example2O3@ C), the test multiplying power is 0.1C, and the specific discharge capacity of the first circle of the material can be seen to be 1874mA h g-11312mA h g is still kept after 200 circles of circulation-1Reversible specific capacity of (B), indicating Fe2O3@ C has good cycle performance.
Example 2
The preparation method comprises the following steps of:
A. adding ferric trichloride hexahydrate and sodium dihydrogen phosphate dihydrate into 300mL of water to obtain a reaction solution; the concentration of ferric trichloride in the reaction liquid is 0.02mol/L, and the concentration of sodium dihydrogen phosphate is 0.45 mmol/L;
and adding the reaction solution into a reaction kettle, carrying out hydrothermal reaction at 105 ℃ for 48h, naturally cooling to room temperature, centrifuging, and washing to obtain the nano spindle ferric oxide.
B. Dispersing 50mg of nano spindle ferric oxide into 200mL of mixed solution composed of isopropanol and water according to the volume ratio of 4:1, ultrasonically stirring for 30min, then adding 2mL of ammonia water and 0.3mL of tetraethyl orthosilicate under the stirring condition, continuously stirring for 4h, centrifuging and washing to obtain a spindle precursor Fe2O3@SiO2；
C. B, mixing the fusiform precursor Fe obtained in the step B2O3@SiO2Dispersing in 100mL of ethanol, then adding 3.2g of PVP, stirring for 18h, centrifuging and washing to finish the modification of the macromolecular surfactant;
the modified fusiform precursor Fe2O3@SiO2Dispersing in 25mL deionized water, adding 0.3mL pyrrole monomer, performing ultrasonic treatment for 30min, dropwise adding 25mL ferric trichloride solution with concentration of 26.6mmol/L under stirring, performing polymerization for 4h, centrifuging, washing, and drying to obtain Fe2O3@SiO2@Ppy；
D. Mixing Fe2O3@SiO2@ Ppy in argon atmosphere, heating to 600 deg.C at a heating rate of 3 deg.C/min, annealing for 4 hr to carbonize polypyrrole to obtain Fe2O3@SiO2@C；
E. Mixing Fe2O3@SiO2@ C is put into 2M sodium hydroxide solution for etching to remove SiO2Namely obtaining the nitrogen-doped carbon-coated ferric oxide cathode material Fe with the interlayer gap structure2O3@C。
FIG. 5 shows an example of a nitrogen-doped carbon-coated iron oxide negative electrode material (Fe) according to the present invention2O3@ C) (fig. 5(a)) and transmission electron micrographs (fig. 5 (b)). The thickness of the interlayer gap structure of the material is 30nm, the thickness of the nitrogen-doped carbon layer is 30nm, the final structure is kept intact, the outer carbon shell is not damaged, and the internal ferric oxide is well protected, so that the cathode material has good cycle stability.
And assembling the battery according to the sequence of the negative electrode shell, the lithium sheet, the diaphragm, the electrolyte, the negative electrode, the gasket, the reed and the positive electrode shell, and carrying out performance test. FIG. 6 shows the negative electrode material (Fe) of this example2O3@ C) in the lithium ion battery, the test multiplying power is 0.1C, and the specific discharge capacity of the first circle of the material can be seen to be 1420mA h g-1After circulating for 200 circles, the 1051mA hour g is still kept-1Reversible specific capacity of (B), indicating Fe2O3@ C has good cycle performance.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A preparation method of a nitrogen-doped carbon-coated ferric oxide negative electrode material for a lithium ion battery is characterized by comprising the following steps of:
the nitrogen-doped carbon-coated ferric oxide negative electrode material for the lithium ion battery is prepared by coating a silicon dioxide layer on the outer surface of nano spindle-shaped ferric oxide to be used as a precursor, coating a layer of conductive polypyrrole on the outer surface of the silicon dioxide layer, finally carbonizing the polypyrrole through annealing, and removing a silicon dioxide interlayer through etching to obtain the nitrogen-doped carbon-coated ferric oxide negative electrode material with an interlayer gap structure; the long axis of the nano spindle-shaped ferric oxide is 100-3000 nm, the short axis of the nano spindle-shaped ferric oxide is 50-1800 nm, the thickness of the interlayer gap structure is 5-30 nm, and the nitrogen-doped carbon layer is amorphous graphite with the thickness of 20-35 nm; the mass percentage of nitrogen-doped carbon in the nitrogen-doped carbon-coated ferric oxide negative electrode material is 34-45%;
the preparation method of the nitrogen-doped carbon-coated ferric oxide negative electrode material for the lithium ion battery comprises the following steps of:
A. synthesizing nano spindle ferric oxide through solvothermal reaction:
adding ferric trichloride and sodium dihydrogen phosphate or sodium hypophosphite into a mixed solution of water and ethanol to obtain a reaction solution; the concentration of ferric trichloride in the reaction liquid is 0.015-0.02 mol/L, and the concentration of sodium dihydrogen phosphate or sodium hypophosphite is 0.1-0.5 mmol/L; in the mixed liquid of water and ethanol, the volume percentage of the ethanol is 0-50%;
adding the reaction solution into a reaction kettle, carrying out hydrothermal reaction at 98-105 ℃ for 48-168 h, then cooling to room temperature, centrifuging, and washing to obtain the nano spindle ferric oxide;
B. dispersing 50mg of nano spindle ferric oxide into 100-200 mL of mixed solution composed of isopropanol and water according to the volume ratio of 4:1, ultrasonically stirring for 10-60 min, then adding 1-5 mL of ammonia water and 0.1-0.6 mL of tetraethyl orthosilicate under the stirring condition, continuously stirring for 4-24 h, centrifuging and washing to obtain a spindle precursor Fe2O3@SiO2；
C. B, mixing the fusiform precursor Fe obtained in the step B2O3@SiO2Dispersing in 100mL of ethanol, then adding 0.5-3.2 g of high molecular surfactant, stirring for 12-48 h, centrifuging, and washing to finish the modification of the high molecular surfactant;
the modified fusiform precursor Fe2O3@SiO2Dispersing in 25mL of deionized water, adding 0.18-0.3 mL of pyrrole monomer, performing ultrasonic treatment for 30min, dropwise adding 25mL of initiator solution with the concentration of 15-27 mmol/L under the stirring condition, performing polymerization for 4-12 h, centrifuging, washing and drying to obtain Fe2O3@SiO2@Ppy；
D. Subjecting said Fe to2O3@SiO2@ Ppy is placed in an inert gas atmosphere, the temperature is raised to 550-650 ℃ at the temperature rise rate of 2-5 ℃/min, annealing is carried out for 2-4 h, polypyrrole is carbonized, and Fe is obtained2O3@SiO2@C；
E. Subjecting said Fe to2O3@SiO2Etching with @ C in alkaline solution to remove SiO2Namely obtaining the nitrogen-doped carbon-coated ferric oxide cathode material Fe with the interlayer gap structure2O3@C。
2. The method of claim 1, wherein: the high molecular surfactant is at least one of polyvinylpyrrolidone, polyacrylamide, hydroxyethyl cellulose and polyoxyethylene copolymer.
3. The method of claim 1, wherein: the initiator is at least one of ammonium persulfate, ferric trichloride, hydrogen peroxide, potassium dichromate and potassium iodate.
4. The method of claim 1, wherein: and E, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution.
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